Crystal structure of trans-W2(CO)6(PPh2H)2(μ2-PPh2)2

The molecular structure of trans-W²(CO)₆(PPh²H)²(₂-PPh²)² was determined by X-ray diffraction analysis. The two tungsten centers, bridged by two diphenylphosphido ligands, are separated by 3.0667(6) Å with W–P–W angles of 77.10(5) and 77.08(5). Average tungsten–phosphorus bond distances are 2.461(17) and 2.4576(21) Å for bridging and terminal phosphorus groups, respectively, with a range of 0.037 Å for the former and 0.001 Å for the latter. The complex crystallizes in the monoclinic space group P2₁/c with a = 19.282(4) Å, b = 12.158(2) Å, c = 21.294(9) Å, = 92.821(4), and Z = 4.     

Carbon–hydrogen and carbon–phosphorus bond cleavage in a triruthenium cluster complex containing dppm: The crystal and molecular structures of Ru3(CO)6{μ 3-OPPh2 C2H(C6H4)PPhCH2PPh}(μ 3-OPPh2)Ph and Ru3(CO)6 {μ-OPPh2C2H(C6H4)PPhO}(μ-PPh2)(μ-PPh2O)

The crystal and molecular structures of Ru₃(CO)₆{μ ₃-OPPh₂C₂H(C₆H₄)PPhCH₂PPh}-(μ ₃-OPPh₂)Ph (1) and Ru₃(CO)₆{μ-OPPh₂C₂H(C₆H₄)PPhO}(μ-PPh₂)(μ-PPh₂O) (2) have been determined by single crystal X-ray diffraction. Both complexes contain oxygen atoms oxidatively inserted into phosphorus–ruthenium bonds, and unique σ/π multidentate ligands formed from C $---{\text{H}}$ H and C $--$ P bond cleavage in bis(diphenylphosphino)acetylene and bis(diphenylphosphino)methane. Complex 1 crystallized in the triclinic space group ${\bar 1}$ , with lattice parameters a = 11.642(4) Å, b = 15.018(5) Å, c =16.587(5) Å, α = 2.48(3)°, β = 76.47(2)°, γ = 70.35(3)°, V = 2651.1(15) ų, Z = 2. Complex 2 crystallized in the centered monoclinic space group, C2/c, with lattice parameters a = 34.467(4) Å, b = 14.274(2) Å, c = 23.258(3) Å, β = 5.29(1)°, V = 11394(3) ų, Z = 8.     

X-ray structure of [Os3(CO)10(μ-Ph2PCH2PPh2)]

Decacarbonyl--bis(diphenylphosphino)methane triosmium crystallizes in the monoclinic space group P2₁/c with a = 24.422(5), b = 12.381(2), c = 24.788(5) Å, = 103.69(3)°, V = 7282 (2) ų, and Z = 8. The molecule consists of a triangular arrangement of osmium atoms with the organic ligand bridging two adjacent osmium atoms at equatorial sites. The Os—Os distances lie in the close range 2.8563(9)–2.8895(11) Å with an average value of 2.87(1) Å.     

Reinvestigation of the reaction of [Ru3(CO)12] with 2-mercaptobenzothiazole: X-ray structure of [(μ-H)2Ru3 (μ-η2-C7H4NS2)(μ3-η2-C7H4NS2)(CO)7]

Treatment of Ru₃(CO)₁₂ with 2-mercaptobenzothiazole at 68°C gave the known compound [(-H)Ru₃(₃-²-C₇H₄NS₂)(CO)₉] 1 and the new compound [(-H)₂Ru₃(-²-C ₇H₄NS₂) (₃-²-C₇H₄NS₂)(CO)₇] 2 in 15 and 10% yields respectively. Compound 2 has been characterized by elemental analysis, infrared, ¹H NMR and mass spectroscopic data together with single crystal X-ray crystallography. It crystallizes in the monoclinic space group C2/c with a = 31.662(6), b = 14.577(3), c = 11.602(2) Å, = 104.15(3)°, Z = 8, and V = 5192.4(2) ų. The compound consists of a Ru₃ triangle with three different Ru-Ru bond lengths [2.75264, 2.79084, 2.97604 Å] and the two 2-mercaptobenzothiazole ligands are differently attached to the metal atoms. Compound 2 is also obtained by the reaction of 1 with excess 2-mercaptobenzothiazole at 68°C.     

Reaction of bis(dimethoxyphosphino)dimethylhydrazine (dmpdmh) with Ru3(CO)12: Evidence for facile ligand fragmentation in Ru3(CO)10(dmpdmh) to give Ru4(CO)12[μ-N(Me)N(Me)], Ru3(CO)11[P(OMe)3], and Ru3(CO)9[μ-P(OMe)3]

Thermolysis of the cluster Ru₃(CO)₁₂ with the bis(phosphanyl)hydrazine ligand (MeO)₂PN (Me)N(Me)P(OMe)₂ (dmpdmh) in toluene at 75°C furnishes the known clusters Ru₄(CO)₁₂ [-N(Me)N(Me)] (2) and Ru₃(CO)₁₁[P(OMe)₃] (3), in addition to the new cluster Ru₃ (CO)₁₀(dmpdmh) (1) and the phosphite-tethered cluster Ru₃(CO)₉[-P(OMe)₃] (4). The simple substitution product Ru₃(CO)₁₀(dmpdmh), a logical intermediate to clusters 2–4, was synthesized by treating Ru₃(CO)₁₂ with Me₃NO in CH₂Cl₂ at room temperature, and independent thermolysis reactions using cluster 1 was shown to yield clusters 2–4. The solid-state structure of clusters 2 and 4 were unequivocally established by X-ray diffraction analysis. Ru₄(CO)₁₂[-N(Me)N(Me)] crystallizes in the orthorhombic space group Pnna (#52), a = 12.913(1), b = 13.3238(6), c = 12.5690(8) Å, V = 2162.5(2) ų, Z = 4, and d _calc = 2.452 g/cm³. Ru₃(CO)₉[-P(OMe)₃] crystallizes in the triclinic space group P a = 9.586(1), b = 14.354(1), c = 14.997(2) Å, = 89.82(1)°, = 98.36(1)°, = 92.010(8)°, V = 2040.4(4) ų, Z = 4, and d _calc = 2.212 g/cm³. The coordination of the dimethylazo linkage to the four ruthenium atoms in 2 and the phosphorus atom and one of the oxygen atoms of the methoxy groups to the three ruthenium centers in 4 are confirmed by X-ray analysis.     

Regiospecific ligand addition to the donor–acceptor compound Ru2(CO)6(bpcd): syntheses and X-ray diffraction structures of Ru2(CO)5L(bpcd) and Ru2(CO)5L[μ-C=C(PPh2)C(O)CH2C}(O)](μ2-PPh2) (where L = PMe3 and tBuNC)

Thermal and Me₃NO-assisted activation of the donor–acceptor complex Ru₂(CO)₆(bpcd) (1) [where bpcd = 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione] with PMe₃ or ^tBuNC affords the mono-substituted complexes Ru₂(CO)₅L(bpcd), as a result of regiospecific ligand attack at the diphosphine-substituted ruthenium center. Solution NMR measurements (¹H and ³¹P) reveal that the PMe₃ derivative exists as a noninterconverting mixture of axial (3a) and equatorial (3e) isomers, with the only the equatorial isomer being observed for Ru₂(CO)₅(^tBuNC)(bpcd) (5). Near-UV irradiation of 1 in the presence of added ligand yields Ru₂(CO)₅L(bpcd), in addition to the known ₂-phosphido complex Ru²(CO)⁶ [-C=C(PPh₂)C(O)CH₂C(O)](₂-PPh₂) (2) and the corresponding phosphido-substituted complexes Ru²(CO)_5L[-{C =C(PPh₂)C(O)CH₂C}(O)]₂-PPh₂)[4 (L = PMe₃); 6 (L = ^tBuNC)]. As with compounds 3a, 3e, and 5, both 4 and 6 exhibit ligand attachment at the diphosphine-substituted ruthenium center. The molecular structures of 3e, 4, 5, and 6 were determined by X-ray crystallography. 3e, as the 1/2 C₆H₆ solvate, crystallizes in the monoclinic space group C2/c: a = 40.573(3) Å, b = 10.2663(9) Å, c = 18.347(1) Å, = 95.371(6)°, V = 7609(1) ų and Z = 8; 4, crystallizes in the monoclinic space group P2₁/n: a = 10.8241(8) Å, b = 18.074(1) Å, c = 19.194(1) Å, = 96.968(6)°, V = 3727.3(5) ų, and Z = 4; 5, as the 1/2CH₂Cl₂ solvate, crystallizes in the monoclinic space group C2/c: a = 40.955(3) Å, b = 9.7230(6) Å, c = 20.542(1) Å, = 106.596(5)°, V = 7839.2(9) ų, and Z = 8; 6, as the 1/2C₅H₁₂ solvate, crystallizes in the monoclinic space group P2₁/c: a = 21.773(2) Å, b = 10.907(3) Å, c = 18.744(4) Å, = 114.68(1)°, V = 4045(1) ų, and Z = 4. The site occupied by the PMe₃ and ^tBuNC ligands in these compounds is discussed relative to the steric size/electronic properties of the ancillary ligand and its interaction with the bpcd ligand.     

Molecular structure of [CpRu(PPh3)2(C6H11SH)]BF4·CH2Cl2

The structure of the [CpRu(PPh₃)₂(C₆H₁₁SH)]BF₄·CH₂Cl₂ complex was determined by X-ray diffraction techniques; triclinic space group ,a=12.567(1),b=13.409(1),c=14.733(1) Å, =95.380(7), =111.041(7), =96.454(8)°,V=2278.5(4) ų,Z=2,R=0.056,R _w=0.088. The Ru is attached to two triphenylphosphine ligands, a cyclopentadienyl and the S atom of the cyclohexylthiol. The Ru–S distance is 2.389(2) Å and the S–H distance is 1.23 Å.     

X-ray crystal structure ofcis-H(Ph3Si)Pt[Ph2P(CH2)4PPh2] ·0.5 C6H6

The title compound, cis-hydrido(triphenylsilyl)-1,4-butanediyl-bis-(diphenylphosphine)platinum(II) (I), crystallizes in the monoclinic space groupP2 ₁/n (No. 14) witha=9.472(4),b=16.924(5),c=25.799(4) Å, β=91.29(3)° andZ=4. The structure was solved using the direct methods and refined by the full-matrix least-squares procedure to yield residuals ofR=0.024 andR _w =0.025 based on 4160 unique reflections. The square-planar geometry about the Pt atom is angularly distorted with P(1)?Pt?P(2) and Si?Pt?P(2) angles of 103.5(1) and 102.1(1)°, respectively. The Pt?P(1) bond is longer than the Pt?P(2) bond due to thetrans influence of the SiPh₃ group. Distortion due to steric bulk of the ligands is accommodated by the opening of the tetrahedral angles at the silicon and phosphorous atoms.     

Bridging and chelating diphosphine ligands in Ru3(μ-H)(μ-N=CPh2)(CO)8(P—P). X-ray diffraction structures of Ru3(μ-H)(μ-N=CPh2)(CO)8(dmpe) and Ru3(μ-H)(μ-N=CPh2)(CO)8(bpcd)

Treatment of the azavinylidene-bridged cluster Ru₃(-H)(-N=CPh₂)(CO)₁₀ (1) with the diphosphine ligand bis(dimethylphosphino)ethane (dmpe) gives Ru₃( -H)(-N=CPh₂)(CO)₈(dmpe) (2) in moderate yield, while the ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) reacts with Ru₃( -H)(-N=CPh₂)(CO)₁₀ in the presence of Me₃NO to furnish Ru₃( -H)(-N=CPh₂)(CO)₈(bpcd) (3) in low yield. Each new cluster has been isolated and characterized in solution by IR and NMR (¹H and ³¹P) spectroscopies, and the coordination mode exhibited by the ancillary diphosphine ligand in 2 and 3 has been established by X-ray crystallography. Ru₃( -H)(-N=CPh₂)(CO)₈(dmpe) crystallizes in the monoclinic space group P2(1)/c, a = 10.791(1) Å, b = 16.377(1) Å, c = 18.148(1) Å, = 96.675(2)°, V = 3185.3(4) ų, Z = 4, D _cacl = 1.791 Mg/m³; R = 0.0360, R _w = 0.0866 for 7522 observed reflections with I > 2(I). Ru₃(-H)(-N=CPh₂)(CO)₈(bpcd) crystallizes, as the CH₂Cl₂ solvate, in the triclinic space group , a = 11.956(1) Å, b = 14.228(1) Å, c = 31.409(3) Å, = 89.377(2)°, = 79.344(2)°, = 77.235(2)°, V = 5118.4(8) ų, Z = 2, D _calc = 1.670 Mg/m³; R = 0.0557, R _w = 0.1069 for 10977 observed reflections with I > 2(I). The structural details of clusters 2 and 3 are contrasted with Ru₃(-H)(-N=CPh₂)(CO)₇(-dppm)(-dppm), which is the only known structurally characterized phosphine-substituted cluster of this genre.     

Reactions of [Mn2(μ-pyS)2(CO)6] with bidentate phosphines: X-ray structure of [Mn(η2-pyS) (η2-dppp)(CO)2] [dppp = Ph2P(CH2)3PPh2, pySH = pyridine-2-thiol]

The dimeric complex [Mn₂(-pyS)₂(CO)₆] (1) reacted with 2 molar equivalents of Ph₂P(CH₂)₃PPh₂ (dppp) and Ph₂P(CH₂)₂PPh₂ (dppe) to give the respective monomeric chelate complexes [Mn(²-pyS)(²-dppp)(CO)₂] (2) and [Mn(²-pyS)(²-dppe)(CO)₂] (3). In contrast, with 2 molar equivalents of Ph₂P(CH₂)₅PPh₂ (dpppe), 1 gave the highly insoluble polymeric complex [Mn(²-pyS)(-dpppe)(CO)₂]n (4). An X-ray structure determination shows that 2 crystallizes in the monoclinic space group P2₁/n with a = 10.721(2) Å, b = 19.712(5) Å, c = 14.846(4) Å, = 109.06(2)°, V = 2965.5(14) ų, and Z = 4. The complex has a distorted octahedral geometry with the dppp ligand, one CO group and the N atom of the chelating pyS ligand occupying equatorial sites, and one CO group and the S atom of the pyS ligand lying in the axial positions.     

Decarbonylation Reaction of [Os3(CO)10(μ-H)(μ-SN2C4H5)]: X-ray Structures of the Two Isomers of [Os3(CO)9(μ-H)(μ 3-η 2-SN2C4H5)]

Abstract  The thermal reaction of [Os₃(CO)₁₀(μ-H)(μ-SN₂C₄H₅)] (1) at 110 °C afforded the new compound [Os₃(CO)₉(μ-H)(μ ₃-η ²-SN₂C₄H₅)] (2) in 84% yield. Compound 2 exists as two isomers, which differ in the disposition of the bridging hydride ligand. Both of the isomers of 2 have been characterized by a combination of elemental analysis, infrared and ¹H NMR spectroscopic data together with single crystal X-ray crystallography. The isomers crystallize together in the triclinic space group P-1 with a = 10.4775(2), b = 13.3056(3), c = 15.0325(3) ?, α = 110.8890(10), β = 99.3880(10), γ = 96.1620(10)°, Z = 2 and V = 1900.31(7) ?³. Index Abstract  The synthesis and the molecular structures of the two isomers of [Os₃(CO)₉(μ-H)(μ ₃-η ²-SN₂C₄H₅)] are described. The isomers differ in the disposition of the hydride ligand.      

Molecular structures of [CpRu(PPh3)(dtoxa-H2O)]BF4 and {[CpRu(PPh3)2]2(μ-dtoxa)}(BF4)2, dtoxa=dithiooxamide

The reaction of [CpRu(PPh₃)₂(n-C₃H₇SH)]BF₄ with dithiooxamide (dtoxa) gave two products: {[CpRu(PPh₃)₂]₂(-dtoxa)} (BF₄)₂,1, and [CpRu(PPh₃)(dtoxa-H₂O)]BF₄,2. The structures of both complexes were determined by X-ray diffraction techniques. Compound1 crystallized in the triclinic space groupP _¯1,a=12.822(4),b=14.16(1),c=23.631(8) Å,=84.57(4),=83.64(3), =83.57(4)°,Z=2,R=0.069,R _w =0.084. The structure of1 shows two CpRu(PPh₃)₂ ⁺ units bridged through the S atoms of the dtoxa ligand. Ru-S distances are 2.377(6)Å for Ru1-S1 and 2.368(6) Å for Ru2-S2. Compound2 crystallized in the monoclinic space groupP2₁/c,a=13.446(3),b=13.461(7),c=31.214(7) Å,=100.78(3)°,Z=8,R=0.054,R _w =0.055. The structure of2 has two molecules in the asymmetric unit. The Ru is chelated to the dtoxa through the S atoms: Ru1-S1, 2.307(4); Ru1-S2, 2.300(4); Ru2-S3, 2.295(4); Ru2-S4, 2.287(4) Å. The coordination sphere of the Ru in2 is completed by a cyclopentadienyl ligand and a triphenylphosphine.     

Synthesis and structural analysis of (μ-SCH2CH2CH2S-μ)Fe2(CO)5(2-C5H4NPPh2)

Treatment of (μ-SCH₂CH₂CH₂S-μ)Fe₂(CO)₆ with equimolar 2-C₅H₄NPPh₂ in the presence of Me₃NO·2H₂O in CH₂Cl₂/MeCN solutions gave the title complex (μ-SCH₂CH₂CH₂S-μ)Fe₂(CO)₅(2-C₅H₄NPPh₂) in 76% yield. The title complex was characterized by spectroscopy as well as by single crystal X-ray diffraction analysis. The molecular structure consists of a butterfly [Fe₂S₂] cluster with propane, five carbonyls, and 2-C₅H₄NPPh₂. In the crystal packing diagram, intermolecular C–H···O hydrogen bonds between phenyl and carbonyl groups stabilize the solid state.     

Diphosphine ligand substitution in H4Ru4(CO)12: X-ray diffraction structures and reactivity studies of the cluster compounds H4Ru4(CO)10(P–P) [where P–P–(Z)–Ph2PCH–CHPPh2, bpcd]

The tetraruthenium cluster H₄Ru₄(CO)₁₂ (1) has been studied for its reactivity with the unsaturated diphosphine ligands (Z)–Ph₂PCH–CHPPh₂ and 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) under thermal, near-UV photolysis, and Me₃NO-assisted activation. All three cluster activation methods promote loss of CO and furnish the anticipated substitution products H₄Ru₄(CO)₁₀[(Z)–Ph₂PCH–CHPPh₂] (2) and H₄Ru₄(CO)₁₀(bpcd) (3) that possess a chelating diphosphine ligand. Clusters 2 and 3 have been characterized in solution by IR and NMR spectroscopies, and these data are discussed with respect to the crystallographically determined structure for both new cluster compounds. The ³¹P NMR spectral data and the solid-state structures confirm the presence of a chelating diphosphine ligand in clusters 2 and 3. Cluster 2 crystallizes in the monoclinic space P2₁/c, a=11.768(6) ?, b=18.521(9) ?, c=20.48(1) ?, β=102.291(8)°, V=4361(4) A³, Z=4, and d _calc=1.726 Mg/m³; R=0.0225, R _w=0.0491 for 6798 reflections with I > 2σ(I). The four bridging hydrides were located in H₄Ru₄(CO)₁₀[(Z)–Ph₂PCH–CHPPh₂] and their adopted positions are discussed relative to the solution ¹H NMR spectrum. H₄Ru₄(CO)₁₀(bpcd) crystallizes in the orthorhombic space Pbca, a=19.072(3) ?, b=20.169(3) ?, c=22.774(3) ?, V=8760(2) A³, Z=8, and d _calc=1.870 Mg/m³; R=0.0428, R _w=0.0896 for 10296 reflections with I > 2σ(I). Sealed NMR tubes containing clusters 2 and 3 were found to be exceeding stable towards near-UV light and temperatures up to ca. 125 °C. The surprisingly robust behavior of 2 and 3 is contrasted with the related cluster Ru₃(CO)₁₀(bpcd) that undergoes fragmentation to the donor-acceptor compound Ru₂(CO)₆(bpcd) and the phosphido-bridged compound Ru₂(CO)₆(μ–PPh₂)[μ–C–C(PPh₂)C(O)CH₂C(O)] under mild conditions. The electrochemical properties of each substituted cluster have been investigated by cyclic voltammetry, and our findings are discussed with respect to the reported electrochemical data on the parent cluster H₄Ru₄(CO)₁₂.

PhPMe2 ligand substitution in the tetracobalt cluster Co4(CO)10(μ4-PPh)2: X-ray diffraction structure of Co4(CO)8(PPhMe2)2(μ4-PPh)2

The thermal substitution chemistry of the tetracobalt cluster Co₄(CO)₁₀(₄-PPh)₂ with the phosphine ligand PhPMe₂ (2.5 equiv) has been explored and found to afford the bis(phosphine)-substituted cluster Co₄(CO)₈(PPhMe₂)₂(₄-PPh)₂ as the major reaction product. The regiochemistry and stereoselectivity exhibited by the two phosphine ligands in Co₄(CO)₈(PPhMe₂)₂(₄-PPh)₂ have been unambiguously established by X-diffraction analysis as having a 1,3-cis orientation. Co₄(CO)₈(PPhMe₂)₂(₄-PPh)₂ crystallizes in the monoclinic space group P2₁/n,a=10.314(1) Å,b=18.051(3) Å,c=21.313(2) Å, =90.10(1)°,V=3968.0(8) ų,Z=4,d _calc=1.590 g cm^–3;R=0.051,R _w=0.042 for 4987 observed reflections withI>3(I). Generalizations concerning the stereochemical disposition of two P-ligands about the Co₄(CO)₈P₂(₄-PPh)₂ (where P=phosphine or phosphite) polyhedron are discussed with respect to the cone angle of the P-ligand and its steric interactions with the capping phenylphosphinidene group.     

Metal-hydroxycarboxylate interactions: syntheses and structures of K2[VO2(C6H6O7)]2·4H2O and (NH4)2[VO2(C6H6O7)]2·2H2O

Potassium and ammonium dimeric (citrato)dioxovanadium(V) hydrate K₂[VO₂(H₂cit)]₂·4H₂O1 and (NH₄)₂[VO₂(H₂cit)]₂·2H₂O2 (H₄cit=citric acid) have been prepared and characterized by X-ray structure analyses. Vanadate1 crystallizes in the monoclinic space groupP2₁/n (No. 14) with unit cell parameters:a=9.304(2),b=11.756(2),c=11.911(2)Å, =111.72(3)°, andD _c=1.911 g/cm³,Z=2; Vanadate2 also crystallizes in the monoclinic space groupP2₁/n with unit cell parameters:a=9.719(2),b=11.111(3),c=11.294(2)Å, =109.03(2)°, andD _c=1.781 g/cm³,Z=2. Each dimer contains a centro-symmetric planar four-member V₂O₂ ring with two exocyclic citrate entities coordinated by the oxygen atoms of the hydroxy-and -carboxylate ligands, while the other two -carboxylate groups remain uncomplexed. Principal dimensions of the V–O bonds are 1.986(4)_av (hydroxy) and 1.980(3)Å(-carboxyl) for vanadate1, 1.988(2)_av (hydroxy) and 1.974(3)Å(-carboxyl) for vanadate2.     

Reactions of [Mn2(μ-pyS)2(CO)6] (pySH=pyridine-2-thiol) with triphenylphosphine (PPh3), diphenylphosphine (PHPh2) and bis(diphenylphosphino)methane (dppm): X-ray crystal structure of [Mn(pyS)(η1-dppm)2(CO)2]

The dimeric complex [Mn₂(-pyS)₂(CO)₆] (1) reacted with 2 M equivalents of both PPh₃ and PHPh₂ to give the respective monomeric phosphine complexes [Mn(pyS)(L)(CO)₃][L = PPh₃ (2) and PHPh₂ (3)]; with 4 M equivalents of dppm, it yielded the complex [Mn(pyS)(¹-dppm)₂(CO)₂](4). An X-ray structure determination of 4 shows that it crystallizes in the monoclinic space group P2₁/n with a = 11.027(3), b = 24.984(7), c = 18.379(5) Å, = 99.870(8)°, V = 4988(2) ų, and Z = 4. The complex has an octahedral geometry with the chelating pyS ligand and two CO groups occupying the equatorial sites and the two monodentate dppm ligands lying in the trans positions.     

孔道结构铁磷酸盐(C4H12N2)2[Fe6(HPO4)2(PO4)6(H2O)2]·H2O的水热合成及热变化过程研究

在与前人不同的条件下水热合成了孔道结构铁磷酸盐(C4H12N2)2[Fe6(HPO4)2(PO4)6(H2O)2]·H2O.用ICP、有机元素分析仪、TG-DTA、变温XRD、变温FT-IR等分析技术对其成份、物相和热变化过程进行了系统研究.结果表明,室温-330℃,化合物失去吸附水,有机模板哌嗪开始氧化脱氢;330-380℃,哌嗪环破坏,大部分有机模板和结晶水脱除,化合物结构骨架明显破坏;470℃化合物完全非晶化;650℃形成FePO4和Fe4(P2O7)3新物相.哌嗪起到平衡电荷和支撑结构的作用.哌嗪环破坏并脱除是导致结构破坏的根本原因.     

Synthesis and X-ray structure of [(μ-H)Ru3(CO)8(μ-Cl)(μ-dppm)] [dppm = bis(diphenylphosphino)methane]

The reaction of [Ru₃(CO)₁₀(-dppm)] 1 with PPhCl₂ in refluxing CHCl₃ results in the isolation of [(-H)Ru₃(CO)₈(-Cl)(-dppm)] 3 in 10% yield. Compound 3, which has been structurally characterized by crystallographic methods, is also formed from the reaction of 1 with H₂ in refluxing CCl₄. The compound crystallizes in the monoclinic space group P2₁/c with a = 16.814(2), b = 18.7590(12), c = 11.486(2) Å, = 97.745(11)°, V = 3589.8(8) ų, and Z = 4. The hydride and chloride ligands bridge the same edge of the triruthenium cluster as the dppm ligand.     

Regiospecific CO substitution in (μ-H)Ru3(μ3− η3-CHCHCMe)(CO)9 by 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione(bpcd). X-ray structure of (μ-H)Ru3(μ3−η3-CHCHCMe)(CO)7(bpcd)⋅MeOH

The triruthenium cluster ( -H)Ru₃( ₃–³-CHCHCMe)(CO)₉ reacts with the diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) in the presence of Me₃NO to afford ( -H)Ru₃( ₃– ³-CHCHCMe)(CO)₇(bpcd) in moderate yield. This new cluster has been isolated and characterized in solution by IR and NMR (¹H, ³¹P) spectroscopies, and the solid-state structure has been established by X-ray crystallography. ( -H)Ru₃( ₃– ³-CHCHCMe)(CO)₇(bpcd) MeOH crystallizes in the triclinic space group P , a = 11.2426(8) Å, b = 11.7141(8) Å, c = 16.195(1) Å, = 102.041(5)°, = 95.128(5)°, = 102.553(6)°, V = 2008.4(3) ų, Z = 2, d _calc. = 1.733 g/cm³; R = 0.0488, R _w = 0.0546 for 2212 observed reflections with I > 3 (I). The X-ray structure reveals that the bpcd ligand is bound exclusively to the Ru₃ core at the ruthenium center coordinated by the terminal CH unit of the -allylic ₃– ³-CHCHCMe moiety.